Structural Characterization of a High-Nuclearity Niobium(V) Carboxylate Cluster Based on Pivalic Acid

We report a novel Nb(V)−carboxylate cluster obtained from reaction of niobium(V) ethoxide and pivalic (trimethylacetic) acid. Single crystal X-ray diffraction data reveal a structure composed of 16 Nb(V) ions featuring oxo-, ethoxy- and pivalate moieties. The new cluster exhibits the highest nuclearity among structurally characterized niobium carboxylates reported to date.     

Versatile low-molecular-weight hydrogelators: achieving multiresponsiveness through a modular design

Multiresponsive low-molecular-weight hydrogelators (LMWHs) are ideal candidates for the development of smart, soft, nanotechnology materials. The synthesis is however very challenging. On the one hand, de novo design is hampered by our limited ability to predict the assembly of small molecules in water. On the other hand, modification of pre-existing LMWHs is limited by the number of different stimuli-sensitive chemical moieties that can be introduced into a small molecule without seriously disrupting the ability to gelate water. Herein we report the synthesis and characterization of multistimuli LMWHs, based on a modular design, composed of a hydrophobic, disulfide, aromatic moiety, a maleimide linker, and a hydrophilic section based on an amino acid, here N-acetyl-L-cysteine (NAC). As most LMWHs, these gelators experience reversible gel-to-sol transition following temperature changes. Additionally, the NAC moiety allows reversible control of the assembly of the gel by pH changes. The reduction of the aromatic disulfide triggers a gel-to-sol transition that, depending on the design of the particular LMWH, can be reverted by reoxidation of the resulting thiol. Finally, the hydrolysis of the cyclic imide moieties provides an additional trigger for the gel-to-sol transition with a timescale that is appropriate for use in drug-delivery applications. The efficient response to the multiple external stimuli, coupled to the modular design makes these LMWHs an excellent starting point for the development of smart nanomaterials with applications that include controlled drug release. These hydrogelators, which were discovered by serendipity rather than design, suggest nonetheless a general strategy for the introduction of multiple stimuli-sensitive chemical moieties, to offset the introduction of hydrophilic moieties with additional hydrophobic ones, in order to minimize the upsetting of the critical hydrophobic-hydrophilic balance of the LMWH.     

Double-differential spectra of the secondary particles in the frame of pre-equilibrium model

An approach was developed to describe the double-differential spectra of secondary particles formed in heavy-ion reactions. Griffin model of nonequilibrium processes was used to account for the nonequilibrium stage of the compound system formation. Simulation of de-excitation of the compound system was carried out using the Monte-Carlo method. Analysis of the probability of neutron, proton, and α-particle emission was performed both in equilibrium, and in the pre-equilibrium stages of the process. Fission and γ-ray emission were also considered after equilibration. The analysis of the experimental data on the double-differential cross sections of p, α particles for the ¹⁶O + ¹¹⁶Sn reaction at the oxygen energy E = 130 and 250 MeV were performed.     

Application of Fluorescence to the Study of Crude Petroleum

Crude petroleum oils are complex mixtures of different compounds (mainly organic), which are obtained from an extensive range of different geological sources. The fluorescence of crude petroleum oils derives largely from the aromatic hydrocarbon fraction, and this fluorescence emission is strongly influenced by the chemical composition (e.g., fluorophore and quencher concentrations) and physical characteristics (e.g., viscosity and optical density) of the oil. The fluorescence spectroscopy (FS) is increasingly used in petroleum technology due the availability of better optical detection techniques, because FS offers high sensitivity, good diagnostic potential, and relatively simple instrumentation. In this work we analyzed crude petroleum at different dilution in Nujol, a transparent mineral oil. The main objective of this work was to verify the possibility to measure crude oil emission spectroscopic without use of volatile solvents. The mixtures of nujol with different -crude oil concentrations were measured with a 10 mm optical path cuvette thus simplifying the fluorescence spectroscopy signal detection. The emission spectra were obtained by exciting the samples with a 400 W Xenon lamp at 350 nm, 450 nm and 532 nm. The emissions of the samples were collected perpendicularly with the excitation axis.     

The synthesis of 4-benzylamino-6-methyl-1H-pyrrolo[3, 2-c]pyridine and 4-benzylamino-6-methyl-1H-pyrrolo[2, 3-b]pyridine

4-Benzylamino-6-methyl-1H-pyrrolo[3,2-c]pyridine ( 2 ) and 4-benzylamino-6-methyl-1H-pyrrolo[2,3-b]pyridine ( 3 ) were synthesized as deaza analogues of the anxiolytic agent 4-benzylamino-2-methyl-7H-pyrrolo[2,3-d]pyrimidine ( 1 ). The 1-deaza analogue (2) was prepared via a multi-step procedure from a pyrrole precursor, 1-benzyl-2-formylpyrrole ( 4 ) while the 3-deaza analogue 3 was synthesized from a pyridine precursor, 2-amino-3,6-dimethylpyridine ( 12 ).     

ACTION DES HYDRAZINES ET DE L'HYDROXYLAMINE SUR QUELQUES PHOSPHONATES β, β-BIFONCTIONNALISES: SYNTHESE DE PHOSPHONOAMINOPYRAZOLES ET ISOXAZOLES

Abstract

Reaction of hydrazines and hydroxylamine with β, β-bifunctionalized phosphonates 1 and 1′ leads to phosphoaminopyrazoles and isoxazoles 2 3, 4 and 5. The structure of all obtained products was confirmed by NMR and IR spectroscopy.     

Fixed or invertible calixarene-based directional shuttles

The first examples of rotaxanes based on calixarenes threaded by dialkylammonium ions, which also represent the first examples of calixarene-based molecular shuttles, are reported. The base/acid treatment demonstrated that these systems act as molecular shuttles, which move between three sites on the axle. When small OMe groups are appended at the calix[6]arene lower rim an unprecedented inversion of its shuttling direction is observed, which occurs through a cone-to-cone inversion of the macrocycle.     

Thermo-optical properties of silver and gold nanofluids

This work focuses on the study of thermal diffusivity and physical properties of nanofluids with very low concentrations of silver or gold nanoparticles. Thermal measurements were performed by means of thermal lens spectroscopy in the dual beam configuration. Improvements of 20 and 16 % in the thermal diffusivity were observed for silver and gold nanofluids, respectively, in comparison with pure water. The estimation of the size distribution of the metallic nanoparticles was obtained through the fitting of the extinction spectra via Mie theory and images of field emission gun scanning electron microscopy.     

Simple circuit to improve electric field homogeneity in contour-clamped homogeneous electric field chambers.

We redesigned contour-clamped homogeneous electric field (CHEF) circuitry to eliminate crossover distortion, to set identical potentials at electrodes of each equipotential pair and to drive pairs with transistors in emitter follower stages. An equipotential pair comprised the two electrodes set at the same potential to provide electric field homogeneity inside of the hexagonal array. The new circuitry consisted of two identical circuits, each having a resistor ladder, diodes and transistors. Both circuits were interconnected by diodes that controlled the current flow to electrodes when the array was energized in the 'A' or 'B' direction of the electric field. The total number of transistors was two-thirds of the total number of electrodes. Average voltage deviation from potentials expected at electrodes to achieve a homogeneous electric field was 0.06 V, whereas 0.44 V was obtained with another circuit that used transistors in push-pull stages. The new voltage clamp unit is cheap, generated homogeneous electric field, and gave reproducible and undistorted DNA band patterns.     

A Three-Dimensional Porous Organic Semiconductor Based on Fully sp2-Hybridized Graphitic Polymer

Dimensionality plays an important role in the charge transport properties of organic semiconductors. Although three-dimensional semiconductors, such as Si, are common in inorganic materials, imparting electrical conductivity to covalent three-dimensional organic polymers is challenging. Now, the synthesis of a three-dimensional π-conjugated porous organic polymer (3D p-POP) using catalyst-free Diels–Alder cycloaddition polymerization followed by acid-promoted aromatization is presented. With a surface area of 801 m² g⁻¹, full conjugation throughout the carbon backbone, and an electrical conductivity of 6(2)×10⁻⁴ S cm⁻¹ upon treatment with I₂ vapor, the 3D p-POP is the first member of a new class of permanently porous 3D organic semiconductors.